Stimulation of wells in nano-darcy shale formations

Abstract

Formulations and methods for stimulating the production from wells in nano-darcy shale formations are described. In one embodiment, the method includes injecting a treatment mixture containing a metal complexing agent into a nano-darcy shale formation adjacent to a well at a pressure below the fracture pressure of the formation. A sufficient contact time is allowed and then the treatment mixture is pumped from the subsurface. This has been shown to stimulate well production in shale formations. Without being held to a particular theory it appears that the metal complexing agent is binding with naturally occurring metals in the shale formation, and particularly divalent metal ions, which are then extracted with the spent fluid. This removal of naturally occurring metals may be increasing the permeability of the formation in the contact region adjacent to the well, thereby causing the observed increased production.

What is claimed is: 
     
       1. A method for stimulating a well in a shale formation comprising:
 providing a treatment mixture containing between about 0.1% and 95% by weight metal complexing agent at a pH of between about 0 and 10; 
 injecting the treatment mixture into the well until at least some of the treatment mixture contacts the shale formation; 
 maintaining the treatment mixture in contact with the shale formation for a contact time of between about 1 minute to 100 days, thereby allowing the metal complexing agent to bind with at least some naturally-occurring metals contained within the shale formation; and 
 removing the treatment mixture from the well after the contact time, thereby removing the bound naturally-occurring metals from the shale formation and thereby improving hydrocarbon production of the well relative to hydrocarbon production immediately prior to stimulating the well. 
 
     
     
       2. The method according to  claim 1 , the metal complexing agent being citric acid. 
     
     
       3. The method according to  claim 1 , the metal complexing agent being ethylenediaminetetraacetic acid (EDTA). 
     
     
       4. The method according to  claim 1 , the metal complexing agent being acetic acid. 
     
     
       5. The method according to  claim 1 , the metal complexing agent includes at least one of ethylenediaminetetraacetic acid (EDTA), propylenediaminetetraacetic acid (PDTA), nitrilotriacetic acid (NTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), cyclohexylenediaminetetraacetic acid (CDTA), diphenylaminesulfonic acid (DPAS), ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA), glucoheptonic acid, gluconic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, aconitic acid, carballylic acid, trimesic acid, isocitric acid, citric acid, or any salt or derivative of any of the previously listed compounds. 
     
     
       6. The method according to  claim 1 , the treatment mixture comprising:
 between about 0.1% and 95% by weight metal complexing agent; 
 between 1 and 10,000 parts per million (ppm) of a corrosion inhibitor; 
 between 1 and 10,000 ppm of a biocide; 
 between 1 and 10,000 ppm of a colloidal silica deposition inhibitor; 
 between 1 and 500 gallons per thousand gallons (gpt) of a mutual solvent; and 
 between 1 and 2000 parts per million of a surfactant. 
 
     
     
       7. The method according to  claim 1 , the treatment mixture further comprising between 0.1 and 95% of acid as pH modifier. 
     
     
       8. The method according to  claim 1 , the injecting operation further comprising:
 alternately injecting a first amount of treatment mixture and a second amount of a diverting mixture into the well. 
 
     
     
       9. The method according to  claim 1 , the injecting operation further comprising:
 injecting the treatment mixture until a pressure within the well reaches a predetermined target pressure; and 
 upon reaching the target pressure, shutting in the well. 
 
     
     
       10. The method according to  claim 1 , further comprising injecting the treatment mixture containing a metal complexing agent in combination with hydraulic fracturing and injecting into the formation in conjunction with propagation of induced fractures, the metal complexing agent including citric acid or EDTA. 
     
     
       11. The method according to  claim 1 , further comprising:
 monitoring at least one of pH and well pressure during the maintaining operation; and 
 initiating the removing operation based on results of the monitoring operation. 
 
     
     
       12. The method according to  claim 1 , the metal complexing agent being selected from glutamic acid diacetic acid (GLDA), methylglycine diacetic acid (MGDA), β-alanine diacetic acid (β-ADA), ethylenediaminedisuccinic acid, S,S-ethylenediaminedi succinic acid (EDDS), iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), polyamino disuccinic acids, N-bis[2-(1,2-dicarboxyethoxy)ethyl]glycine (BCA6), N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid (BCA5), N-bis[2-(1,2-dicarboxyethoxy)ethyl]methylglycine (MCBA5), N-tris[(1,2-dicarboxyethoxy)ethyl]amine (TCA6), N-methyliminodiacetic acid (MIDA), iminodiacetic acid (IDA), N-(2-acetamido)iminodiacetic acid (ADA), hydroxymethyl-iminodiacetic acid, 2-(2-carboxyethylamino) succinic acid (CEAA), 2-(2-carboxymethylamino) succinic acid (CMAA), diethylenetriamine-N,N″-disuccinic acid, triethylenetetramine-N,N′″-disuccinic acid, 1,6-hexamethylenediamine-N,N′-disuccinic acid, tetraethylenepentamine-N,N″″-disuccinic acid, 2-hydroxypropylene-1,3-diamine-N,N′-disuccinic acid, 1,2-propylenediamine-N,N′-disuccinic acid, 1,3-propylenediamine-N,N′-disuccinic acid, cis-cyclohexanediamine-N,N′-disuccinic acid, trans-cyclohexanediamine-N,N′-disuccinic acid, ethylenebis(oxyethylenenitrilo)-N,N′-disuccinic acid, glucoheptanoic acid, cysteic acid-N,N-diacetic acid, cysteic acid-N-monoacetic acid, alanine-N-monoacetic acid, N-(3-hydroxysuccinyl) aspartic acid, N-[2-(3-hydroxysuccinyl)]-L-serine, aspartic acid-N,N-diacetic acid, aspartic acid-N-monoacetic acid, any salt thereof, any derivative thereof, or any combination thereof. 
     
     
       13. The method according to  claim 1 , the metal complexing agent being selected from acetic acid, acrylates, dihydroxymaleic acid, salts of dihydroxymaleic acid, EDTA (ethylenediamine tetraacetic acid), salts of EDTA, erythorbic acid, erythroboric acid, formic acid, gluconodeltalactone, GLDA (glutamic acid N,N-diacetic acid), salts of GLDA, HEDTA (hydroxyethylenediamine triacetic acid), salts of HEDTA, HEIDA (disodium ethanoldiglycine), salts of HEIDA, MGDA (methylglycine N,N-diacetic acid), salts of MGDA, NTA (nitriolotriacetic acid), organic metal complexers, ligands, porphyrins, pigments, peptides, saccharides, nucleic acids, phosphonic acid, polyacrylic acid and citric acid in an amount sufficient to sequester at least a portion of a metal compound.